Quantifying the Effect of Guest Binding on Host Environment.

The environment around a host-guest complex is defined by intermolecular interactions between the complex, solvent molecules, and counterions. These interactions govern both the solubility of these complexes and the rates of reactions occurring within the host molecules and can be critical to catalytic and separation applications of host-guest systems. However, these interactions are challenging to detect using standard analytical chemistry techniques. Here, we quantify the hydration and ion pairing of a FeII4L4 coordination cage with a set of guest molecules having widely varying physicochemical properties. The impact of guest properties on host ion pairing and hydration was determined through microwave microfluidic measurements paired with principal component analysis (PCA). This analysis showed that introducing guest molecules into solution displaced counterions that were bound to the cage, and that the solvent solubility of the guest has the greatest impact on the solvent and ion-pairing dynamics surrounding the host. Specifically, we found that when we performed PCA of the measured equivalent circuit parameters and the solubility and dipole moment, we observed a high (>90%) explained variance for the first two principal components for each circuit parameter. We also observed that cage-counterion pairing is well-described by a single ion-pairing type, with a one-step reaction model independent of the type of cargo, and that the ion-pairing association constant is reduced for cargo with higher water solubility. Quantifying hydration and cage-counterion interactions is a critical step to building the next generation of design criteria for host-guest chemistries.

Selective adsorption of arsenic over phosphate by transition metal cross-linked chitosan.

The ability of transition metal chitosan complexes (TMCs) of varying valence and charge to selectively adsorb As(III) and As(V) over their strongest adsorptive competitor, phosphate is examined. Fe(III)-chitosan, Al(III)-chitosan, Ni(II)-chitosan, Cu(II)-chitosan, and Zn(II)-chitosan are synthesized, characterized via Attenuated Total Reflectance-Fourier Transform Infrared spectroscopy (ATR-FTIR) and X-ray Diffractometry (XRD), and their selective sorption capabilities towards As(III) and As(V) in the presence of phosphate are evaluated. It was found that the stability of the metal-chitosan complexes varied, with Al(III)- and Zn(II)-chitosan forming very unstable complexes resulting in precipitation of gibbsite, and Wulfingite and Zincite, respectively. Cu(II)-, Ni(II)-, and Fe(III)-chitosan formed a mixture of monodentate and bidentate complexes. The TMCs which formed the bidentate complex (Cu(II)-, Ni(II)-, and Fe(III)-) showed greater adsorption capability for As(V) in the presence of phosphate. Using the binary separation factor ∝t/c, it can be shown that only Fe(III)-chitosan is selective for As(V) and As(III) over phosphate. Density Functional Theory (DFT) modeling and extended X-ray adsorption fine structure (EXAFS) determined that Fe(III)-chitosan and Ni(II)-chitosan adsorbed As(V) and As(III) via inner-sphere complexation, while Cu(II)-chitosan formed mainly outer-sphere complexes with As(V) and As(III). These differences in complexation likely result in the observed differences in selective adsorption capability towards As(V) and As(III) over phosphate. It is hypothesized that the greater affinity of Fe(III)- and Ni(II)-chitosan towards As(V) and As(III) compared to Cu(II)-chitosan is due to their forming less-stable, more reactive chitosan complexes as predicted by the Irving Williams Series.

Hydrophobic CuO Nanosheets Functionalized with Organic Adsorbates.

A new class of hydrophobic CuO nanosheets is introduced by functionalization of the cupric oxide surface with p-xylene, toluene, hexane, methylcyclohexane, and chlorobenzene. The resulting nanosheets exhibit a wide range of contact angles from 146° (p-xylene) to 27° (chlorobenzene) due to significant changes in surface composition induced by functionalization, as revealed by XPS and ATR-FTIR spectroscopies and computational modeling. Aromatic adsorbates are stable even up to 250-350 °C since they covalently bind to the surface as alkoxides, upon reaction with the surface as shown by DFT calculations and FTIR and 1H NMR spectroscopy. The resulting hydrophobicity correlates with H2 temperature-programmed reduction (H2-TPR) stability, which therefore provides a practical gauge of hydrophobicity.

Fundamental Role of Oxygen Stoichiometry in Controlling the Band Gap and Reactivity of Cupric Oxide Nanosheets.

CuO is a nonhazardous, earth-abundant material that has exciting potential for use in solar cells, photocatalysis, and other optoelectronic applications. While progress has been made on the characterization of properties and reactivity of CuO, there remains significant controversy on how to control the precise band gap by tuning conditions of synthetic methods. Here, we combine experimental and theoretical methods to address the origin of the wide distribution of reported band gaps for CuO nanosheets. We establish reaction conditions to control the band gap and reactivity via a high-temperature treatment in an oxygen-rich environment. SEM, TEM, XRD, and BET physisorption reveals little to no change in nanostructure, crystal structure, or surface area. In contrast, UV-vis spectroscopy shows a modulation in the material band gap over a range of 330 meV. A similar trend is found in H2 temperature-programmed reduction where peak H2 consumption temperature decreases with treatment. Calculations of the density of states show that increasing the oxygen to copper coverage ratio of the surface accounts for most of the observed changes in the band gap. An oxygen exchange mechanism, supported by (18)O2 temperature-programmed oxidation, is proposed to be responsible for changes in the CuO nanosheet oxygen to copper stoichiometry. The changes induced by oxygen depletion/deposition serve to explain discrepancies in the band gap of CuO, as reported in the literature, as well as dramatic differences in catalytic performance.

Shape-Dependent Surface Reactivity and Antimicrobial Activity of Nano-Cupric Oxide.

Shape of engineered nanomaterials (ENMs) can be used as a design handle to achieve controlled manipulation of physicochemical properties. This tailored material property approach necessitates the establishment of relationships between specific ENM properties that result from such manipulations (e.g., surface area, reactivity, or charge) and the observed trend in behavior, from both a functional performance and hazard perspective. In this study, these structure-property-function (SPF) and structure-property-hazard (SPH) relationships are established for nano-cupric oxide (n-CuO) as a function of shape, including nanospheres and nanosheets. In addition to comparing these shapes at the nanoscale, bulk CuO is studied to compare across length scales. The results from comprehensive material characterization revealed correlations between CuO surface reactivity and bacterial toxicity with CuO nanosheets having the highest surface reactivity, electrochemical activity, and antimicrobial activity. While less active than the nanosheets, CuO nanoparticles (sphere-like shape) demonstrated enhanced reactivity compared to the bulk CuO. This is in agreement with previous studies investigating differences across length-scales. To elucidate the underlying mechanisms of action to further explain the shape-dependent behavior, kinetic models applied to the toxicity data. In addition to revealing different CuO material kinetics, trends in observed response cannot be explained by surface area alone. The compiled results contribute to further elucidate pathways toward controlled design of ENMs.

Polyphenolic disaccharides endow proteins with unusual resistance to aggregation.

Protein aggregation is a common problem during the purification and formulation of therapeutic proteins. Here we report that polyphenolic disaccharides are unusually effective at preventing protein aggregation. We find that two polyphenolic glycosides-naringin and rutin-endow diverse proteins with the ability to unfold without aggregating when heated, as well as the ability to refold without aggregating when cooled at low glycoside concentrations (<5 mM). This extreme solubilizing activity is a synergistic combination of the glycone and aglycone moieties, as combinations of polyphenols and sugars fail to suppress aggregation. Moreover, the activity of polyphenolic disaccharides is remarkably specific since their monosaccharide counterparts (as well as other common excipients such as arginine, trehalose, and cyclodextrin) fail to prevent aggregation at similar concentrations (<25 mM). We expect that polyphenolic disaccharides will be valuable additives for enhancing the solubility of proteins in applications plagued by protein aggregation.

Polyphenolic glycosides and aglycones utilize opposing pathways to selectively remodel and inactivate toxic oligomers of amyloid ß.

Substantial evidence suggests that soluble prefibrillar oligomers of the Aß42 peptide associated with Alzheimer's disease are the most cytotoxic aggregated Aß isoform. Limited previous work has revealed that aromatic compounds capable of remodeling Aß oligomers into nontoxic conformers typically do so by converting them into off-pathway aggregates instead of dissociating them into monomers. Towards identifying small-molecule antagonists capable of selectively dissociating toxic Aß oligomers into soluble peptide at substoichiometric concentrations, we have investigated the pathways used by polyphenol aglycones and their glycosides to remodel Aß soluble oligomers. We find that eleven polyphenol aglycones of variable size and structure utilize the same remodeling pathway whereby Aß oligomers are rapidly converted into large, off-pathway aggregates. Strikingly, we find that glycosides of these polyphenols all utilize a distinct remodeling pathway in which Aß oligomers are rapidly dissociated into soluble, disaggregated peptide. This disaggregation activity is a synergistic combination of the aglycone and glycone moieties because combinations of polyphenols and sugars fail to disaggregate Aß oligomers. We also find that polyphenolic glycosides and aglycones use the same opposing pathways to remodel Aß fibrils. Importantly, both classes of polyphenols fail to remodel nontoxic Aß oligomers (which are indistinguishable in size and morphology to Aß soluble oligomers) or promote aggregation of freshly disaggregated Aß peptide; thus revealing that they are specific for remodeling toxic Aß conformers. We expect that these and related small molecules will be powerful chemical probes for investigating the conformational and cellular underpinnings of Aß-mediated toxicity.

Nano-structural effects on Hematite (α-Fe2O3) nanoparticle radiofrequency heating.

Nano-sized hematite (α-Fe2O3) is not well suited for magnetic heating via an alternating magnetic field (AMF) because it is not superparamagnetic-at its best, it is weakly ferromagnetic. However, manipulating the magnetic properties of nano-sized hematite (i.e., magnetic saturation (Ms), magnetic remanence (Mr), and coercivity (Hc)) can make them useful for nanomedicine (i.e., magnetic hyperthermia) and nanoelectronics (i.e., data storage). Herein we study the effects of size, shape, and crystallinity on hematite nanoparticles to experimentally determine the most crucial variable leading to enhancing the radio frequency (RF) heating properties. We present the synthesis, characterization, and magnetic behavior to determine the structure-property relationship between hematite nano-magnetism and RF heating. Increasing particle shape anisotropy had the largest effect on the specific adsorption rate (SAR) producing SAR values more than 6 × greater than the nanospheres (i.e., 45.6 ± 3 W/g of α-Fe2O3 nanorods vs. 6.89 W/g of α-Fe2O3 nanospheres), indicating α-Fe2O3 nanorods can be useful for magnetic hyperthermia.

Catalytic manganese oxide nanostructures for the reverse water gas shift reaction.

Understanding the fundamental structure-property relationships of nanomaterials is critical for many catalytic applications as they comprise of the catalyst designing principles. Here, we develop efficient synthetic methods to prepare various MnO2 structures and investigate their catalytic performance as applied to the reverse Water Gas Shift (rWGS) reaction. We show that the support-free MnO derived from MnO2 1D, 2D and 3D nanostructures are highly selective (100% CO2 to CO), thermally stable catalysts (850 °C) and differently effective in the rWGS. Up to 50% conversion is observed, with a H2/CO2 feed-in ratio of 1 : 1. From both experiments and DFT calculations, we find the MnO2 morphology plays a critical role in governing the catalytic behaviors since it affects the predominant facets exposed under reaction conditions as well as the intercalation of K+ as a structural building block, substantially affecting the gas-solid interactions. The relative adsorption energy of reactant (CO2) and product (CO), ΔE = Eads(CO2) -Eads(CO), is found to correlate linearly with the catalytic activity, implying a structure-function relationship. The strong correlation found between Eads(CO2) -Eads(CO), or more generally, Eads(R) -Eads(P), and catalytic activity makes ΔE a useful descriptor for characterization of efficient catalysts involving gas-solid interactions beyond the rWGS.

Tuning two-dimensional phase formation through epitaxial strain and growth conditions: silica and silicate on NixPd1-x(111) alloy substrates.

Two-dimensional (2D) materials can have multiple phases close in energy but with distinct properties, with the phases that form during growth dependent on experimental conditions and the growth substrate. Here, the competition between 2D van der Waals (VDW) silica and 2D Ni silicate phases on NixPd1-x(111) alloy substrates was systematically investigated experimentally as a function of Si surface coverage, annealing time and temperature, O2 partial pressure, and substrate composition and the results were compared with thermodynamic predictions based on density functional theory (DFT) calculations and thermochemical data for O2. Experimentally, 2D Ni silicate was exclusively observed at higher O2 pressures (∼10-6 Torr), higher annealing temperatures (1000 K), and more prolonged annealing (10 min) if the substrate contained any Ni and for initial Si coverages up to 2 monolayers. In contrast, decreasing the O2 pressure to ∼10-8 Torr and restricting the annealing temperature and time enabled 2D VDW silica formation. Amorphous 2D VDW silica was observed even when the substrate composition was tuned to lattice match crystalline 2D VDW silica. The trend of decreased O2 pressure favoring 2D VDW silica was consistent with the theoretical predictions; however, theory also suggested that sufficient Si coverage could avoid Ni silicate formation. The effect of epitaxial strain on 2D Ni silicate was investigated by modifying the solid solution alloy substrate composition. It was found that 2D Ni silicate will stretch to match the substrate lattice constant up to 1.12% tensile strain. When the lattice mismatch was over 1.40%, incommensurate crystalline domains were observed, indicating relaxation of the overlayer to its favored lattice constant. The limited epitaxial strain that could be applied was attributed to a combination of the 2D silicate stiffness, the insensitivity of its bonding to the substrate to its alignment with the substrate, and its lack of accessible structural rearrangements that can reduce the strain energy. The results demonstrate how the resulting 2D material can be manipulated through the growth conditions and how a solid solution alloy substrate can be used to maximize the epitaxial strain imparted to the 2D system.

Hard templating ultrathin polycrystalline hematite nanosheets: effect of nano-dimension on CO2 to CO conversion via the reverse water-gas shift reaction.

Understanding how nano-dimensionality impacts iron oxide based catalysis is central to a wide range of applications. Here, we focus on hematite nanosheets, nanowires and nanoparticles as applied to catalyze the reverse water gas shift (RWGS) probe reaction. We introduce a novel approach to synthesize ultrathin (4-7 nm) hematite nanosheets using copper oxide nanosheets as a hard template and propose a reaction mechanism based on density functional theory (DFT) calculations. Hematite nanowires and nanoparticles were also synthesized and characterized. H2 temperature programmed reduction (H2-TPR) and RWGS reactions were performed to glean insights into the mechanism of CO2 conversion to CO over the iron oxide nanomaterials and were compared to H2 binding energy calculations based on density functional theory. While the nanosheets did exhibit high CO2 conversion, 28% at 510 °C, we found that the iron oxide nanowires had the highest CO2 conversion, reaching 50% at 750 °C under atmospheric pressure. No products besides CO and H2O were detected.